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This work presents a spectroscopic and theoretical study of several energy materials using synchrotron-based techniques. Two classes of materials are studied: solids that have reported photocatalytic properties, and lithium compounds that are thought to form during the cycling of modern battery electrodes. An overview of synchrotron soft X-ray spectroscopic techniques is presented, along with the theory and procedures associated with performing such measurements. These measurements are compared to density functional theory (DFT) calculations, as implemented by the WIEN2k package, along with a description of the DFT method. Calculated electronic structure is shown to be a useful aid in interpreting the results of X-ray emission and X-ray near-edge absorption measurements (XES and XANES), allowing conclusions about the physical structure and properties of the materials to be reached. Two photocatalytic systems are outlined, the first of which is a solid solution of GaN and ZnO (GaN:ZnO) that exhibits an unexpected reduction in band gap. By carefully comparing common hybridized features from O, N and Zn core emission lines, a binding energy picture of the valence and conduction bands of GaN:ZnO is constructed, allowing its band gap reduction to be described as a consequence of heterojunctions between predominantly GaN and ZnO regions within the solid solution. This description attempts to resolve controversy in the literature regarding the origin of the band gap reduction, as well as to rule out a hypothesized oxynitride superlattice structure as the explanation. The second photocatalytic system studied is a carbon nitride derivative, poly(triazine imide) (PTI) that displays high crystallinity and that could be very inexpensive to produce due to its elemental abundance. Through resonant excitation, two inequivalent N sites in PTI can be probed by X-ray emission spectroscopy, indicating the material is not a conjugated polymer like other reported carbon nitrides. The band gap of the system is observed to decrease in response to disordered Li loading, an e ect that is con rmed by DFT calculation. Several potential disorder models of the Li loading of PTI are investigated with DFT force minimization in order to choose a structural candidate capable of producing calculated X-ray spectra that agree with our measurements. The presented lithium study attempts to use a modern soft X-ray absorption facility to characterize the Li surface by-products inherent to the charge-discharge cycling of a battery electrode. A survey of potential Li compounds was performed using Li K-edge XANES will be compared to DFT calculations and X-ray Raman Scattering measurements performed by collaborators in the future. Correlating measurements of the survey compounds with charge-cycled electrode measurements will be an area for future work.

Master of Science / Department of Electrical and Computer Engineering / William B. Kuhn / RF frequency synthesizer systems are prevalent in today’s electronics. In a synthesizer there is a sensitive analog oscillator that may be affected by two different types of noise. The first is random noise injection from active devices. This results in phase noise in the synthesizer’s spectrum. The second noise source is deterministic. A digital frequency divider with high-amplitude switching is an example of such a deterministic source. This noise enters the system through various forms of electric or magnetic field coupling and manifests itself as spurs or pulling. Both forms of noise can adversely affect system performance. We will first summarize methods for reducing noise. These already known steps have to do with layout techniques, device geometry, and general synthesizer topologies. Then we will show ways to isolate noisy interfering circuits from the sensitive analog systems. Finally, we present some considerations for reducing the effects of random noise. A power supply filter can improve the effects of deterministic noise such as undesired signals on the supply line. We show several ways to improve the rejection of high frequency supply noise (characterized by the power supply rejection ratio or PSRR) through the design of a voltage regulator. The emphasis is on new techniques for obtaining good PSRR at S-band frequencies and above. To validate the techniques, we designed a regulator in Peregrine Semiconductor’s .25µm ULTRA CMOS Silicon on Sapphire process. It produces a 2.5V output with an input ranging from 2.6V to 5V and has a maximum current sourcing of 70mA. The regulator’s low drop out performance is 60mV with no load and it achieves a power supply ripple reduction of 29.8 dB at 500 MHz. To address random noise in synthesizers, the thesis provides preliminary investigation of an oscillator topology change that has been proposed in the literature. This proposed change reduces the phase noise of the oscillator within the overall system. A differential cross-coupled design is the usual topology of choice, but it is not optimal for noise performance. We investigate current noise injection in the traditional design and present an updated design that uses a differential Colpitts oscillator as an alternative to classic cross-coupled designs.

Organic solar cells have been showing promise as a way of producing renewableenergy with the help of light, flexible, and production effective materials.The efficiencies and lifetimes reached in organic solar cells have steadily beenincreasing over the years as more research in the field is being conducted.One way of increasing the efficiency in organic solar cell devices is introducingan interlayer between the photoactive material and the anode, referred toas the ’hole transport layer’. Most commonly used as a hole transport layer isthe material PEDOT:PSS, which offers desired properties such as transparency,simple processing and good ohmic contact between anode and photoactive material.PEDOT:PSS is also known to be a degradation site in organic solar cells,as it will corrode the electrode in the presence of water.This project has consisted of investigating PEDOT:PSS along with two othercandidates that may one day come to replace PEDOT:PSS as the most commonlyused material, molybdenum trioxide (MoO3) and phosphomolybdic acid(PMA). The aim was to investigate how the different materials energy bandstructure would be affected upon exposure to sunlight, air and annealing, byobserving the work function under different conditions.

Second generation solar cells based on thin film semiconductors emerged as a result of the past ten years of intense research in the thin film preparation technology. Thin film solar cell technology can be cost effective as it uses comparatively cheap materials suitable for solar building integration. Chemical Vapour Deposition (CVD) is a well-known method for the deposition of high quality thin films. This thesis describes the synthesis of novel tin(II)dithiocarbamate [Sn(S2CNEt2)2] and bis(diphenylphosphinediselenoato) tin(II) [Sn(Ph2PSe2)2] and these complexes as single source precursor for the deposition of SnS and SnSe and by using the combination of [Sn(Ph2PSe2)2] with [Cu(acac)2], Cu2SnSe3 thin films were deposited by AACVD. By using suitable combinations of metal complexes ([nBu2Sn(S2CNEt2)2], [Cu(S2CNEt2)2] [Zn(S2CNEt2)2] [Zn(Se2CNEt2)2] [Zn(acac)2], [Sn(OAc)4], [Cu(PPh3){Ph2P(Se)NP(Se)Ph2}] thin films and nanocomposites of CZTS, CFTS, CZTSe, CFTSe, CZFTS, , CZFTSe, CZTSSE, CFTSSe and CZFTSSe were prepared. The effect of precursor concentration and deposition temperature on the structure, morphology and composition of the thin films were studied in detail using by powder X-ray diffraction (p-XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and elemental mapping. This thesis addressing the structural inhomogeneity, control of growth and material characterization is expected to yield closer performance parity between CZTS-Se and CIGS solar cells. A series of systematic experiments were carried out. Through AACVD and simple solvothermal methods CZFTS nanoparticles and thin films were prepared. The simple, potentially, low-cost nature of the CZTS nanoparticles and the enhancement of charge carrier mobility achieved suggest that these nanoparticles have potential in the improvement of OFETs and perhaps other organic electronic devices.

Magister Scientiae - MSc / In this research, novel hybrid perovskite materials were synthesized, characterized and applied in photovoltaic cells (PVCs) to enhance the performance of PVCs. Mixed-organic-cations tin halide perovskites (MOCTPs) were successfully synthesized using sol-gel method. These MOCTPs include guanidinium dimethylammonium tin iodide ([GA][(CH3)2NH2]SnI3) and guanidinium ethylmmonium tin iodide ([GA][CH3CH2NH3]SnI3). The MOCTPs were studied in comparison to their single-organic-cation tin perovskites (SOCTPs), which include guanidinium tin iodide (GASnI3), ethylammonium tin iodide ([CH3CH2NH3]SnI3) and dimethylammonium tin iodide [(CH3)2NH2]SnI3. High Resolution Scanning Electron Microscopy (HR SEM) of the five perovskite materials showed good crystallinity and tetragonal and hexagonal cubic shapes, characteristic of perovskites. These shapes were also confirmed from High Resolution Transmission Electron Microscopy (HR TEM), and the internal structure of the perovskites gave similar zone axes (ZAs) with those obtained from X-ray Diffraction (XRD). XRD showed tetragonal lattice shape for these perovskite materials. Fourier Transform Infrared (FTIR) demonstrated similar functional groups for both the SOCTPs and MOCTPs. FTIR bands that were observed are; N-H, C-H sp3, C-H aldehyde, N-H bend, C-N sp3 and N-H wag. From the 13C Nuclear Magnetic Resonance (NMR) results, the carbon atom of guanidinium iodide precursor shifts from downfield to upfield position, e.g. from 110.57 ppm to 38.49 ppm in GASnI3 SOCTP. This confirms a shift upfield of the carbon atom in guanidinium iodide precursor as it bonded to Sn metal in the perovskite chemical structure. Similar behavior was also observed for the NMR spectra of [GA][CH3CH2NH3]SnI3 MOCTP, where C-2 and C-3 atoms of ethylammonium iodide precursor shifted upfield from 37.03 ppm to 15.69 ppm and 16.06 ppm to 14.39 ppm respectively.

As far as we know, we only have one planet to live on, with a delicate atmospheric system providing us safety and life. Global CO2 emissions continue to plague the environment of Earth, primarily due to the processing of fossil fuels, deforestation, and industrialization. There are several avenues of pursuing CO2 reutilization, each having their own benefits and limitations. Direct and indirect thermochemical approaches of CO2 conversion boast of efficient CO2 conversion rates but have limitations associated with the use of renewable hydrogen and high temperatures of operation. The work in this dissertation investigates low temperature photocatalytic CO2 conversion, a simple principle, which provides opportunity for fuel production while harvesting solar energy. Large scale implementation of this process has been plagued by limitations such as fast electron/hole recombination rates, poor quantum efficiency, product selectivity, catalyst stability, and the band gap energy (Eg) being too large to harvest solar light. Our long term goals and applications look to utilize sustainable fuel generation in-situ on Mars for human exploration. We must use available Mars resources to generate fuel to save launch and resource costs from Earth, utilizing the Sun, Mars atmospheric CO2 (95%), and H2O that can be harvested from subsurface ice. Visible light activated catalysts are needed for applications of CO2 conversion on Earth and Mars due to the intensity and abundance of visible light available in the solar spectrums. The dissertation presents the development of photocatalysts for CO2 reduction in the presence of H2O under visible light irradiation. Detailed chemical analysis and characterization were performed on the photocatalysts for improved understanding of material design, including optical and elemental properties, charge transport, stability, catalytic function and scalability. Induced defects and impurities were implemented to understand Eg tunability. Introducing defects through impurities reduced the electron confinement effects in some cases, increasing the photocatalytic activity. Three material regimes were synthesized, tuned, and tested for catalytic function. The first was a series of (ZnO)1-x(AlN)x, materials that had not been synthesized previously, nor ever demonstrated in CO2 and H2O under solar irradiation. The Zn:Al materials were derived from layered double hydroxides. The second material set was (ZnO)1-x(GaN)x, also derived from layered double hydroxides. To the best of our knowledge, these Zn:Ga materials were demonstrated for the first time in CO2 reduction to CO under visible light without the use of any noble metal co-catalysts or dopants. The third set of materials were MoS2 nanoflowers synthesized via chemical vapor deposition that, to our pleasant surprise, produced thinly stacked sheets in the form of nanoflowers that contained large edge-site exposure, which was vastly different from the morphology of commercially purchased MoS2. The preliminary results from this work have demonstrated that tunable band gap energy is achievable. The (ZnO)1-x(AlN)x Eg ranged from 2.84 to 3.25 eV. The Zn:Al solid solution materials were tuned by increasing nitridation time, and varying the cationic ratio. Increasing the cationic ratio in this study more than tripled CO production under solar light irradiation compared to lower cationic ratios. The (ZnO)1-x(GaN)x, materials had a Eg range from 2.33 eV to 2.59 eV. The Eg was also easily tunable from varying nitriding time and cationic ratio. The highest CO production rate was the Zn:Ga cationic ratio of 3:1 at 20 min of nitriding time at 100 °C, which produced 1.06 µmol-g-1-h-1. This production was higher than both of our controlled TiO2 experiments, and other reported pure TiO2 solar photoreaction experiments. The results indicate a delicate balance of nitridation and Zn:M3+ ratio should be selected, along with precursor material cation ratios in order to obtain the desired final product and crystal structure. The controlled introduction of imperfections or crystal defects through MoS2 synthesis variations also revealed the tuning ability of flake edge morphology, nanoflower diameter, stacked-sheet thickness, optical Eg and catalytic activity. The nanoflower Eg ranged from 1.38 to 1.83 eV, and the production rates of CO nearly doubled when post treating the nanoflowers in a reduction step. These developments support tunable gas phase photocatalytic activity and can be enhanced further for further photocatalytic reactions, optoelectronics and field emitter applications. The photoreactor studies indicated that careful tuning of the parent material is imperative to understand before adding a co-catalyst or doping process, as the edge site morphology, crystal phase stability, and strain-induced defects impact the photocatalytic performance.

TiO2 photocatalysis is been widely studied for air and water purification applications; titanium dioxide is the most used semiconductor principally because its low cost, stability and chemical properties. However it only utilizes the UV portion of the solar spectrum as an energy source (less than 4% of the total sunlight energy). This behavior is due to its high band gap value of 3.2 eV. The modification of light harvesting properties of TiO2 by doping has become an important research topic to achieve an efficient operating range under UV and visible light. In addition, the structure and surface properties of photocatalysts play an important role. This thesis explores the effects of Zn doped TiO2, prepared by the sol-gel method, on its photocatalytic activity to decompose organics and the characterization of the doped samples. Since this study is part of a collaborative initiative, the samples were synthesized and provided by Dr. A. R. Phani from the Department of Physics, University of L'Aquila. Preliminary examination revealed a relatively low photocatalytic efficiency of the samples. The objective is to modify/improve its properties by high energy ball milling which is expected to generate accumulations of defects, particle size reduction and an increase in the active surface area. The characterization of doped and mechanochemically treated materials will be analyzed by optical diffuse reflectance measurements and optical absorption calculations using the Kubelka-Munk approach. The phase structure and particle size of the materials will be determined using X-ray diffraction (XRD). The BET surface area of the samples will be obtained using an Autosorb instrument. The photocatalytic properties will be studied by the analysis of decomposition of Methyl Orange in an aqueous solution. An aqueous photocatalytic tubular reactor with capability of operation using UV and/or fluorescent light will be designed and built.

This paper involves the calculation for composition of different layer used in laser structure and the simulation of cavity, formed by creating air columns in the InGaAsP medium, for square lattice. The aim of this project is to fabricate approximately zero threshold current lasers. This project involves FDTD simulation for optimizing dimension of the device, fabrication of laser structure and finally characterization of the device structure. / Singapore-MIT Alliance (SMA)

A near infrared waveguide photodetector in Si-based ternary Si₁−x−yGexCy alloy was demonstrated for 0.85~1.06 µm wavelength fiber-optic interconnection system applications. Two sets of detectors with active absorption layer compositions of Si₀.₇₉Ge₀.₂C₀.₀₁ and Si₀.₇₀Ge₀.₂₈C₀.₀₂ were designed. The active absorption layer has a thickness of 120~450 nm. The external quantum efficiency can reach ~3% with a cut-off wavelength of around 1.2 µm. / Singapore-MIT Alliance (SMA)